The present invention relates to pro-fragrance compounds useful in laundry detergent compositions. The pro-fragrance compounds comprise a fragrance raw material component and a solubility or substantivity component which can be independently adjusted to meet the specific requirements of the formulator. The pro-fragrance compounds are especially useful for delivering a xe2x80x9cthrough the washxe2x80x9d fresh-like or clean-like fragrance to fabric which remains on the fabric and is continuously released for extended periods after the conclusion of the laundry cycle.
In addition to the removal of stains, dirt, soil, grime, and grease from fabric, laundry detergent formulators have attempted to deliver a xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d odor to washed clothing to provide an olfactory aesthetic benefit and to serve as a signal that the product is effective. Laundry detergent compositions, including rinse-added fabric softeners and dryer-added substrates, are currently formulated with perfume and fragrance ingredients which are aesthetically pleasing to the consumer but which fail to deliver a prolonged xe2x80x9cfragrancexe2x80x9d or xe2x80x9cpleasurable smellxe2x80x9d to the finished, cleaned fabric.
Among the most readily perceived fragrance materials are the perfume xe2x80x9ctopxe2x80x9d and xe2x80x9cmiddlexe2x80x9d notes which are highly volatile compounds and which are usually detectable at low levels. However, these highly volatile materials are typically lost either during the prolonged heating which takes place in an automatic dryer or they lack the substantivity necessary to deposit onto the fabric surface and are therefore lost during the laundry rinsing process.
Attempts have been made to deliver perfume ingredients onto fabric which can survive the laundry rinsing and drying cycles and therefore provide a residual xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d odor to the washed material. However, none of these attempts have suitably provided fabric with a protracted release of fragrance raw materials which provide a xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d smell for a period up to two weeks after washing. There has especially been a long felt need to deliver certain tertiary alcohol fragrance raw materials inter alia linalool and dihydromyrcenol.
Accordingly, there remains a need in the art for a fragrance delivery system wherein perfume raw materials are delivered to fabric by way of a laundry detergent composition which provides the cleaned clothing or fabric with a xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d smell for a period up to two weeks after washing. Also, there is a need for fragrance releasing compounds which deliver a xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d fragrance in which the solubility and substantivity properties of the compound can be varied to match various formulation and delivery parameters inter alia compatibility with surface active adjuncts and fabric type. In addition, there is a need for a fragrance delivery system suitable for providing sustained release or enhanced longevity fragrances to a variety of personal care and personal hygiene products inter alia deodorants, body lotions or creams, and shampoos.
The following relate to the subject matter of fragrance ingredients. U.S. Pat. No. 5,232,612 Trinh et al., issued Aug. 3, 1996; U.S. Pat. No. 5,506,201 McDermott et al., issued Apr. 9, 1996; U.S. Pat. No. 5,378,468 Suffis et al., issued Jan. 3, 1995; U.S. Pat. No. 5,266,592 Grub et al., issued Nov. 30, 1993; U.S. Pat. No. 5,081,111 Akimoto et al., issued Jan. 14, 1992; U.S. Pat. No. 4,994,266 Wells, issued Feb. 19, 1991; U.S. Pat. No. 4,524,018 Yemoto et al., issued Jun. 18, 1985; U.S. Pat. No. 3,849,326 Jaggers et al., issued Nov. 19, 1974; U.S. Pat. No. 3,779,932 Jaggers et al., issued Dec. 18, 1973; JP 07-179,328 published Jul. 18, 1995; JP 05-230496 published Sept. 7, 1993; WO 96/14827 published May 23, 1996; WO 95/04,809 published Feb. 16, 1995; and WO 95/16660 published Jun. 22, 1995. In addition, P. M. Muller, D. Lamparsky Perfumes Art, Science, and Technology Blackie Academic and Professional, (New York, 1994) is included herein by reference.
The present invention meets the aforementioned needs in that it has been surprisingly discovered that certain linear acetals and ketals can be used to deliver perfume or fragrance raw materials onto fabric xe2x80x9cthrough the washxe2x80x9d from a single precursor pro-fragrance molecule having variable fabric substantivity, variable solubility as well as variable fragrance release rate. These pro-fragrances can be used to deliver tertiary alcohol raw materials as well as primary and secondary fragrance raw material alcohols which impart a xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d aesthetic odor benefit to fabric or to human skin when the skin is contacted with a personal care or personal hygiene product inter alia deodorants, body lotions or creams, and shampoos, which comprises the pro-fragrances of the present invention. In addition to the short-term pleasurable odor benefits, the pro-fragrances according to the present invention continue to release their fragrance raw materials for as long as several weeks depending upon the structure of the pro-accord.
The pro-fragrances described herein comprise fragrance raw materials in a stable, releasable form. The pro-fragrance containing laundry detergent compositions of the present invention can comprise any number of pro-fragrances and are suitable for delivery of any type of fragrance xe2x80x9ccharacteristicxe2x80x9d desired by the formulator.
The first aspect of the present invention relates to pro-fragrance compounds having the formula: 
R1 and R2 are each independently:
a) C8-C22, preferably C8-C12 linear or branched alkyl;
b) C8-C22, preferably C8-C12 linear or branched alkenyl;
c) C2-C20, preferably C2-C12, more preferably C2-C6 substituted or unsubstituted alkyleneoxy;
d) C3-C20, preferably C3-C12, more preferably C3-C6 substituted or unsubstituted alkyleneoxyalkyl;
e) C7-C20, preferably C7-C12, more preferably C7 substituted or unsubstituted alkylenearyl;
f) C6-C20, preferably C6-C10, more preferably C6 substituted or unsubstituted aryloxy;
g) C7-C20, preferably C8-C12, more preferably C8 substituted or unsubstituted alkyleneoxyaryl;
h) C7-C20, preferably C7-C11, more preferably C7 oxyalkylenearyl;
i) C2-C20, preferably C2-C12, more preferably C2-C6 alkylenecarboxy having the formula:
xe2x80x94(CH2)xR9 
wherein R9 is xe2x80x94CHO, xe2x80x94CO2M; xe2x80x94CO2R10, xe2x80x94CONH2, xe2x80x94CONHR10, xe2x80x94CONR10R11, and mixtures thereof; wherein R10 and R11 are each independently C1-C12 linear or branched alkyl, preferably methyl or ethyl;
M is hydrogen or a salt forming cation, preferably sodium or potassium; x is an integer from 1 to 19;
j) an anionic unit having the formula:
xe2x80x94(CH2)yR12 
wherein R12 is xe2x80x94SO3M, xe2x80x94OSO3M, xe2x80x94PO3M, xe2x80x94OPO3M, or mixtures thereof;
wherein M is hydrogen, one or more salt forming cations sufficient to satisfy charge balance, preferably sodium or potassium; or mixtures thereof; y is an interger from 1 to about 22;
k) and mixtures thereof;
R3 and R4 are each independently hydrogen, methyl, ethyl, propyl, phenyl, benzyl, and mixtures thereof.
The present invention also relates to laundry detergent compositions which comprise the pro-fragrance linear acetals and ketals described herein. A further aspect of the present invention is the use of the linear acetal and ketal pro-fragrances of the present invention as a post-laundry xe2x80x9cfreshening agentxe2x80x9d for use on fabric which has been laundered but which has not been worn for an extended period of time. A yet further aspect of the present invention is the use of the pro-fragrances of the present invention in rinse-added compositions and in dryer-added compositions. These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The pro-fragrances of the present invention comprise a fragrance raw material component and a substantivity or solubility component. The fragrance raw material component can be any perfume or any xe2x80x9cfragrance raw material alcoholxe2x80x9d which the formulator wishes to deliver to the fabric surface for subsequent release after the laundry cycle. In addition, the pro-fragrances comprise a substantivity or solubility component wherein the proper choice of group allows the formulator to control the solubility of the pro-fragrance in water, the degree of substantivity of the pro-fragrance for fabric, or the bulk properties of the material. The manipulation of the pro-fragrance bulk properties will allow the formulator to produce a pro-fragrance which is more easily admixed into a particular type of laundry detergent, for example, liquid, granular, high density, encapsulated-component, etc.
Once the laundry process is complete and the pro-fragrance has been suitably delivered to the fabric, the pro-fragrance begins to release the fragrance raw material and because this release of material is protracted, the fabric remains xe2x80x9cfreshxe2x80x9d and xe2x80x9ccleanxe2x80x9d smelling longer. However, pro-fragrances according to the present invention can also be designed to be activated by a change in pH or to be moisture or xe2x80x9cheat activatedxe2x80x9d so as to release a xe2x80x9cfreshening scentxe2x80x9d to the fabric during drying. Therefore, heat-activated pro-fragrances can be delivered to the fabric surface. This results in a fabric having high xe2x80x9cinitial scentxe2x80x9d as well as the lower xe2x80x9ccleanxe2x80x9d and xe2x80x9cfreshxe2x80x9d scent obtained by the protracted release of non-activated pro-fragrances. What is meant herein by xe2x80x9cheat activatedxe2x80x9d pro-fragrances are compounds which have a higher release rate of their fragrance materials after exposure to elevated temperatures. Therefore the formulator may achieve an initial high fragrance delivery coupled with the longer term sustained release.
The pro-fragrances of the present invention are therefore a means for delivering a desired fragrance raw material onto fabric and thereby providing the fabric with a longer and more sustained xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d smell. For the purposes of the present invention the term xe2x80x9cfragrance raw material alcoholxe2x80x9d is defined as xe2x80x9can alcohol generally having a molecular weight greater than or equal to 100 g/mol which provides a fragrance, scent, smell, odor, or character which is generally deemed pleasurable to the senses.xe2x80x9d
Most of the fragrance raw materials which comprise the pro-fragrances of the present invention are not deliverable as individual compounds to fabric via the laundry cycle either due to solubility factors (lost or rinsed away during the laundry cycles), substantivity factors (do not sufficiently adhere to fabric surface), or volatility factors (evaporation during the drying cycle). Therefore, the pro-fragrances described herein are a means for delivering certain fragrance raw materials to fabric which could not have previously been effectively or efficiently delivered. In fact, the tertiary alcohol fragrance raw materials are more suitably delivered by the pro-fragrances of the present invention than by conventional pro-fragrances.
The xe2x80x9cfragrance raw materialsxe2x80x9d which comprise the preferred embodiments are fragrance raw material alcohols. A listing of common fragrance raw material alcohols can be found in various reference sources, for example, xe2x80x9cPerfume and Flavor Chemicalsxe2x80x9d, Vols. I and II; Steffen Arctander Allured Pub. Co. (1994) and xe2x80x9cPerfumes: Art, Science and Technologyxe2x80x9d; Mxc3xcller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) all of which are incorporated herein by reference.
Those skilled in the art of detergent compositions will recognize that the terms xe2x80x9csubstantivexe2x80x9d and xe2x80x9csubstantivityxe2x80x9d refer to the propensity of a compound to adhere to, associate with, or deposit upon a surface, preferably the surface of fabric. Therefore, compounds which are more substantive more readily adhere to fabric surface. However, substantive compounds, in general, do not react with the surface onto which they deposit.
The pro-fragrances of the present invention are derivatives of aldehydes and ketones having the formula: 
R1 and R2 are each independently:
a) C8-C22, preferably C8-C12 linear or branched alkyl;
b) C8-C22, preferably C8-C12 linear or branched alkenyl;
c) C2-C20, preferably C2-C12, more preferably C2-C6 substituted or unsubstituted alkyleneoxy;
d) C3-C20, preferably C3-C12, more preferably C3-C6 substituted or unsubstituted alkyleneoxyalkyl;
e) C7-C20, preferably C7-C12, more preferably C7 substituted or unsubstituted alkylenearyl;
f) C6-C20, preferably C6-C10, more preferably C6 substituted or unsubstituted aryloxy;
g) C7-C20, preferably C8-C12, more preferably C8 substituted or unsubstituted alkyleneoxyaryl;
h) C7-C20, preferably C7-C11, more preferably C7 oxyalkylenearyl;
i) C2-C20, preferably C2-C12, more preferably C2-C6 alkylenecarboxy having the formula:
xe2x80x94(CH2)xR9 
wherein R9 is xe2x80x94CHO, xe2x80x94CO2M; xe2x80x94CO2R10, xe2x80x94CONH2, xe2x80x94CONHR10, xe2x80x94CONR10R11, and mixtures thereof; wherein R10 and R11 are each independently C1-C12 linear or branched alkyl, preferably methyl or ethyl;
M is hydrogen or a salt forming cation, preferably sodium or potassium; x is an integer from 1 to 19;
j) an anionic unit having the formula:
xe2x80x94(CH2)yR12 
wherein R12 is xe2x80x94SO3M, xe2x80x94OSO3M, xe2x80x94PO3M, xe2x80x94OPO3M, or mixtures thereof;
wherein M is hydrogen, one or more salt forming cations sufficient to satisfy charge balance, preferably sodium or potassium; or mixtures thereof; y is an interger from 1 to about 22;
k) and mixtures thereof;
R3 and R4 are each independently hydrogen, methyl, ethyl, propyl, phenyl, benzyl, and mixtures thereof.
More preferably R1 and R2 are 2,4-dimethyl-3-cyclo-hexene-1-methyl (Floralol), 2,4-dimethyl cyclohexane methyl (Dihydro floralol), 5,6-dimethyl-1-methylethenyl-bicyclo[2.2.1]hept-5-ene-2-methyl (Arbozol), 2,4,6-trimethyl-3-cyclohexene-1-methyl (Isocyclo geranyl), 4-(1-methylethyl)cyclohexylmethyl (Mayol), a-3,3-trimethyl-2-norboranylmethyl, 1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methyl, 2-phenylethyl, 2-cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-methylphenyl)ethyl, 2-(p-methylphenyl)ethyl, 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-ethyl (nopyl), 2-(4-methylphenoxy)ethyl, 3,3-dimethyl-D2-b-norbomanylethyl, 2-methyl-2-cyclohexylethyl, 1-(4-isopropylcyclohexyl)ethyl, 1-phenyl-1-hydroxyethyl, 1,1-dimethyl-2-phenylethyl, 1,1-dimethyl-2-(4-methylphenyl)ethyl, 1-phenylpropyl, 3-phenylpropyl, 2-phenylpropyl (Hydrotropic Alcohol), 2-(cyclododecyl)-propan-1-yl (Hydroxyambran), 2,2-dimethyl-3-(3-methylphenyl)propan-1-yl (Majantol), 2-methyl-3-phenylpropyl, 3-phenyl-2-propen-1-yl (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-1-yl (methylcinnamyl alcohol), a-n-pentyl-3-phenyl-2-propen-1-yl (a-amylcinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propyl, 3-(4-methylcyclohex-3-ene)butyl, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)butyl, 2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-1-yl, 3-methyl-2-buten-1-yl, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2buten-1-yl, 3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-yl, 2-methyl-4-phenylbutan-2-yl, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, cis-3-pentenyl, 3-methylpentyl, 3-methyl-3-penten-1-yl, 2-methyl-4-phenylpentyl (Pamplefleur), 3-methyl-5-phenylpentyl (Phenoxanyl), 2-methyl-5-phenylpentyl, 2-methyl-5-(2,3-dimethyltricyclo-[2.2.1.0(2,6)]hept-3-yl)-2-penten-1-yl (santalyl), 4-methyl-1-phenyl-2-pentyl, (1-methyl-bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-yl, 3-methyl-1-phenylpent-3-yl, 1,2-dimethyl-3-(1-methylethenyl)cyclopent-1-yl , 2-isopropyl-4-methyl-2-hexenyl, cis-3-hexen-1-yl, trans-2-hexen-1-yl, 2-isopropenyl-5-methyl-4-hexen-1-yl (Lavandulyl), 2-ethyl-2-prenyl-3-hexenyl (silwanol), 2-ethylhexyl, 1-hydroxymethyl-4-isopropenyl-1-cyclohexenyl (Dihydrocuminyl), 1-methyl-4-isopropenylcyclohex-6-en-2-yl (carvenyl), 6-methyl-3-isopropenylcyclohex-1-yl, 1-methyl-4-isopropenylcyclohex-3-yl, 4-iso-propyl-1-methylcyclohex-3-yl, 4-tert-butylcyclohexyl, 2-tert-butylcyclohexyl, 2-tert-butyl-4-methylcyclohexyl, 4-isopropylcyclohexyl, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-yl, 2-(5,6,6-trimethyl-2-norbornyl)cyclohexyl, isobornylcyclohexyl, 3,3,5-trimethylcyclohexyl, 1-methyl-4-isopropylcyclohex-3-yl (menthol), 1,2-dimethyl-3-(1-methylethyl)-cyclohexan-1-yl, heptyl, 2,4-dimethylhept-1-yl, 2,4-dimethyl-2,6-heptandienyl, 6,6-dimethyl-2-oxymethylbicyclo[3.1.1]hept-2-en-1-yl (myrtenyl), 4-methyl-2,4-heptadien-1-yl, 3,4,5,6,6-pentamethyl-2-heptyl, 3,6-dimethyl-3-vinyl-5-hepten-2-yl, 6,6-dimethyl-3-hydroxy-2-methylenebicyclo[3.1.1]-heptyl, 1,7,7-trimethylbicyclo-[2.2.1]hept-2-yl, 2,6-dimethylhept-2-yl, 2,6,6-trimethylbicyclo[1.3.3]hept-2-yl, octyl, 2-octenyl, 2-methyloctan-2-yl, 2-methyl-6-methylene-7-octen-2-yl (myrcenyl), 7-methyloctan-1-yl, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-octenyl, 3,7-dimethyl-6-octen-1-yl (citronellyl), 3,7-dimethyl-2,6-octadien-1-yl (geranyl), 3,7-dimethyl-2,6-octadien-1-yl (neryl), 3,7-dimethyl-1,6-octadien-3-yl (linalyl), 3,7-dimethyloctan-1-yl (pelagryl), 3,7-dimethyloctan-3-yl (tetrahydrolinalyl), 2,4-octadien-1-yl, 3,7-dimethyl-6-octen-3-yl, 2,6-dimethyl-7-octen-2-yl, 2,6-dimethyl-5,7-octadien-2-yl, 4,7-dimethyl-4-vinyl-6-octen-3-yl, 3-methyloctan-3-yl, 2,6-dimethyloctan-2-yl, 2,6-dimethyloctan-3-yl, 3,6-dimethyloctan-3-yl, 2,6-dimethyl-7-octen-2-yl, 2,6-dimethyl-3,5-octadien-2-yl (mugyl), 3-methyl-1-octen-3-yl, 7-hydroxy-3,7-dimethyloctanalyl, 3-nonyl, 6,8-dimethylnonan-2-yl, 3-(hydroxymethyl)-2-nonanone, 2-nonen-1-yl, 2,4-nonadien-1-yl, 2,6-nonadien-1-yl, cis-6-nonen-1-yl, 3,7-dimethyl-1,6-nonadien-3-yl, decyl, 9-decenyl, 2-benzyl-M-dioxa-5-yl, 2-decen-1-yl, 2,4-decadien-1-yl, 4-methyl-3-decen-5-yl, 3,7,9-trimethyl-1,6-decadien-3-yl (isobutyl linallyl), undecyl, 2-undecen-1-yl, 10-undecen-1-yl, 2-dodecen-1-yl, 2,4-dodecadien-1-yl, 2,7,11-trimethyl-2,6,10-dodecatrien-1-yl (farnesyl), 3,7,11-trimethyl-1,6,10,-dodecatrien-3-yl, 3,7,11,15-tetramethylhexadec-2-en-1-yl (phytyl), 3,7,11,15-tetramethylhexadec-1-en-3-yl (iso phytol), p-methoxybenzyl (anisyl), para-cymen-7-yl (cuminyl), 4-methylbenzyl, 3,4-methylenedioxybenzyl, 2-(methyl)carboxy-1-hydroxyphenyl, 2-(benzyl)carboxy-1-hydroxyphenyl, 2-(cis-3-hexenyl)-carboxy-1-hydroxyphenyl, 2-(n-pentyl)carboxy-1-hydroxyphenyl, 2-(2-phenylethyl)carboxy-1-hydroxyphenyl, 2-(n-hexyl)carboxy-1-hydroxyphenyl, 2-methyl-5-isopropyl-1-hydroxyphenyl, 4-ethyl-2-methoxyphenyl, 4-allyl-2-methoxy-1-hydroxyphenyl (eugenyl), 2-methoxy-4-(1-propenyl)-1-hydroxyphenyl (isoeugenyl), 4-allyl-2,6-dimethoxy-1-hydroxyphenyl, 4-tert-butyl-1-hydroxyphenyl, 2-ethoxy-4-methyl-1-hydroxyphenyl, 2-methyl-4-vinyl-1-hydroxyphenyl, 2-isopropyl-5-methyl-1-hydroxyphenyl (thymyl), 2-(isopentyl)-carboxy-1-hydroxyphenyl, 2-(ethyl)carboxy-1-hydroxyphenyl, 6-(methyl)carboxy-2,5-dimethyl-1,3-dihydroxyphenyl, 5-methoxy-3-methyl-1-hydroxyphenyl, 2-tert-butyl-4-methyl-1-hydroxyphenyl, 1-ethoxy-2-hydroxy-4-propenylphenyl, 4-methyl-1-hydroxyphenyl, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthyl, 2,5,5-trimethyl-octahydro-2-naphthyl, 1,3,3-trimethyl-2-norbornyl (fenchyl), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-yl, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-yl, 2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuranyl, b-caryophyllenyl, and mixtures thereof.
Most preferred R1 and R2 are 3,7-dimethyl-1,6-octadien-3-ol (linalool, as a racemic mixture or as each optical isomer alone), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol, as a racemic mixture or as each optical isomer alone), and mixtures thereof.
R3 and R4 are each independently hydrogen, methyl, ethyl, propyl, phenyl, benzyl, and mixtures thereof, preferably at least one R3 or R4 is not hydrogen atom, more preferably one R3 or R4 is hydrogen atom and the other R3 or R4 is methyl.
For the purposes of the present invention substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula: 
wherein R13 is hydrogen; R14 is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 10.
For the purposes of the present invention substituted or unsubstituted alkyleneoxyalkyl are defined as moieties having the formula: 
wherein R13 is hydrogen, C1-C18 alkyl, C1-C4 alkoxy, and mixtures thereof; R14 is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 9 and the index y is from 1 to about 18.
For the purposes of the present invention substituted or unsubstituted alkylenearyl units are defined as moieties having the formula: 
wherein R13 and R14 are each independently hydrogen, hydroxy, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (xe2x80x94CHO; xe2x80x94CO2H; xe2x80x94CO2Rxe2x80x2; xe2x80x94CONH2; xe2x80x94CONHRxe2x80x2; xe2x80x94CONRxe2x80x22;
wherein Rxe2x80x2 is C1-C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is from 1 to about 14.
For the purposes of the present invention substituted or unsubstituted aryloxy units are defined as moieties having the formula: 
wherein R13 and R14 are each independently hydrogen, hydroxy, C1-C4 alkyl, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (xe2x80x94CHO; xe2x80x94CO2H; xe2x80x94CO2Rxe2x80x2; xe2x80x94CONH2; xe2x80x94CONHRxe2x80x2; xe2x80x94CONRxe2x80x22; wherein Rxe2x80x2is C1-C15 linear or branched alkyl), amino, alkylamino, and mixtures thereof.
For the purposes of the present invention substituted or unsubstituted alkyleneoxyaryl units are defined as moieties having the formula: 
wherein R13 and R14 are each independently hydrogen, hydroxy, C1-C4 alkyl, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (xe2x80x94CHO; xe2x80x94CO2H; xe2x80x94CO2Rxe2x80x2; xe2x80x94CONH2; xe2x80x94CONHRxe2x80x2; xe2x80x94CONRxe2x80x22; wherein Rxe2x80x2 is C1-C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is from 1 to about 14.
For the purposes of the present invention substituted or unsubstituted oxyalkylenearyl units are defined as moieties having the formula: 
wherein R13 and R14 are each independently hydrogen, hydroxy, C1-C4 alkyl, C1-C4 alkoxy, nitrilo, halogen, nitro, carboxyl (xe2x80x94CHO; xe2x80x94CO2H; xe2x80x94CO2Rxe2x80x2; xe2x80x94CONH2; xe2x80x94CONHRxe2x80x2; xe2x80x94CONRxe2x80x22; wherein Rxe2x80x2 is C1-C12 linear or branched alkyl), amino, alkylamino, and mixtures thereof, w is from 1 to about 14.
The pro-fragrances of the present invention release xe2x80x9cfragrance raw material alcoholsxe2x80x9d which provide a pleasurable xe2x80x9cfreshxe2x80x9d and/or xe2x80x9ccleanxe2x80x9d smell or scent to fabric to which the pro-fragrances are applied. Non-limiting examples of alcohols suitably released by the hydrolysis of the orthoester pro-fragrances include methanol, 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-1-methylethenylbicyclo[2.2.1]hept-5-ene-2-methanol (Arbozol), 2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol), 4-(1-methylethyl)cyclohexanemethanol (Mayol), a-3,3-trimethyl-2-norborane methanol, 1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methanol, ethanol, 2-phenylethanol, 2-cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p-methylphenyl)ethanol, 6,6-dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanol (nopol), 2-(4-methylphenoxy)ethanol, 3,3-dimethyl-D2-b-norbornane ethanol, 2-methyl-2-cyclohexylethanol, 1-(4-isopropylcyclohexyl)-ethanol, 1-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-methyl-phenyl)ethanol, n-propanol, 2-propanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran), 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol), a-n-pentyl-3-phenyl-2-propen-1-ol (a-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propanol, n-butanol, 2-butanol, 3-methylbutanol, 3-(4-methylcyclohex-3-ene)butanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)butanol, 2-ethyl-4-(2,2,3-trimethyl-cyclopent-3-enyl)-2-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, pentanol, cis-3-pentenol, 3-methyl-pentanol, 3-methyl-3-penten-1-ol, 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5-phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo[2.2.1.0(2,6)]hept-3-yl)-2-penten-1-ol (santalol), 4-methyl-1-phenyl-2-pentanol, (1-methyl-bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol, 3-methyl-1-phenylpentan-3-ol, 1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol, 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene (Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 1-methyl-4-iso-propenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclo-hexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 4-isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-ol, heptanol, 2,4-dimethylheptan-1-ol, 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-2-oxymethylbicyclo [3.1.1]hept-2-ene(myrtenol), 4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethyl-3-hydroxy-2-methylenebicyclo [3.1.1]heptane, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2,6-dimethylheptan-2-ol, 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol), 7-methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol (geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 3,7-dimethyl-1,6-octadien-3-ol (linalool), 3,7-dimethyloctan-1-ol (pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol, 3,7-dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-5,7-octadien-2-ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol, 3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadien-2-ol (muguol), 3-methyl-1-octen-3-ol, 7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-nonen-1-ol, 6,8-dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone, 2-nonen-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-decadien-3-ol (isobutyl linalool), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 2,4-dodecadien-1-ol, 2,7,11-trimethyl-2,6,10-dodecatrien-1-ol (farnesol), 3,7,11-trimethyl-1,6,10,-dodecatrien-3-ol, 3,7,11,15-tetramethylhexadec-2-en-1-ol (phytol), 3,7,11,15-tetramethylhexadec-1-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), para-cymen-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4-(1-propenyl)phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxy benzoate, ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy-1-methylbenzene, 2-tert-butyl-4-methyl-1-hydroxybenzene, 1-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3,3-trimethyl-2-norbornanol (fenchol), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuran, b-caryophyllene alcohol, and mixtures thereof.
Preferred alcohols released by the pro-fragrance compounds of the present invention are 4-(1-methylethyl)cyclohexanemethanol (mayol), 2,4-dimethyl-3-cyclohexen-1-ylmethanol (floralol), 2,4-dimethylcyclohex-1-ylmethanol (dihydrofloralol), 2,4,6-trimethyl-3-cyclohexen-1-ylmethanol (isocyclogeraniol), 2-phenylethanol, 1-(4-isopropylcyclohexyl)ethanol (mugetanol), 2-(o-methylphenyl)ethanol (ortho-hawthanol), 2-(m-methylphenyl)ethanol (meta-hawthanol), 2-(p-methylphenyl)-ethanol (para-hawthanol), 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (majantol), 3-phenyl-2-propen-1-ol (cinnamic alcohol), 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (santalaire), 3-methyl-5-phenylpentan-1-ol (phenoxanol), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol(ebanol), 2-methyl-4-phenylpentan-1-ol (pamplefleur), cis-3-hexen-1-ol, 3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol (geraniol, nerol or mixtures thereof), 7-methoxy-3,7-dimethyloctan-2-ol (osyrol), 3,7-dimethyl-1,6-octadien-3-ol (linalool), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol) 6,8-dimethylnonan-2-ol, cis-6-nonen-1-ol, 2,6-nonadien-1-ol, 4-methyl-3-decen-5-ol(undecavertol), benzyl alcohol, 2-methoxy-4-(1-propenyl)phenol (isoeugenol), 2-methoxy-4-(2-propenyl)phenol (eugenol), 4-hydroxy-3-methoxybenzaldehyde (vanillin), and mixtures thereof. More preferably 3,7-dimethyl-1,6-octadien-3-ol (linalool), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), and mixtures thereof.
According to the present invention all isomers of a fragrance raw material whether in the form of the pro-fragrance or the released fragrance raw material, are suitable for use in the present invention. When optical isomers are possible, fragrance raw materials may be included as either the separate chemical isomer or as the combined racemic mixture. For example, 3,7-dimethyl-6-octen-1-ol, commonly known by those of ordinary skill in the art as b-citronellol or cephrol, comprises a pair of optical isomers, R-(+)-b-citronellol and S-(xe2x88x92)-b-citronellol. Each of these materials separately or as a racemic pair are suitable for use as fragrance raw materials in the present invention. However, those skilled in the art of fragrances, by utilization of the present invention, should not disregard any olfactory differences that individual optical isomers impart. By way of example, carvone, 2-methyl-5-(1-methylethenyl)-2-cyclohexene-1-one exists as two isomers; d-carvone and l-carvone. d-Carvone is found in oil of caraway and renders a completely different fragrance from l-carvone which is found in spearmint oil. According to the present invention a pro-fragrance which releases d-carvone will result in a different fragrance than one which releases l-carvone. The same applies to l-carvone.
Similarly, the pro-fragrances of the present invention may form diasteriomers when more than one chiral center is present in the molecules. According to the present invention, no single isomer or isomer pair is favored over another single isomer or isomer pair, however, if the formulator chooses one isomer or pair of isomers over the other because of their fragrance xe2x80x9ccharacterxe2x80x9d or other bulk property characteristic, the choice does not diminish the value of the other remaining isomer or isomer pair for the purposes of the present invention.
The ketals and acetals of the present invention can be modified by the formulator to provide highly substantive pro-fragrance compounds capable of delivering both linalool and tetrahydromyrcenol to fabric surfaces for subsequent release after the laundry process has concluded. An example of a linalool-containing pro-fragrance which comprises a highly substantive moiety has the formula: 
wherein an octadecyl moiety provides for increased fabric substantivity.
An example of a dihydromyrcenol-containing pro-fragrance which comprises a highly substantive moiety has the formula: 
wherein a decyl moiety provides for increased fabric substantivity.
Fragrance raw materials may be too hydrophilic for direct formulation into laundry detergent compositions. The present invention provides compounds which have highly hydrophobic moieties which aid in the solublizing of the substrate as well as the substantivity. An example of a linalool-containing pro-fragrance which comprises a highly water soluble moiety has the formula: 
wherein a C6 alkyl E4 moiety provides for increase fabric substantivity.
In addition, the present invention relates to fragrance delivery systems useful in laundry detergent compositions, and rinse-added and dryer-added fabric conditioning compositions. The fragrance delivery systems of the present invention provide slow, sustained release of fragrance raw materials which provide the clothing or fabric article with a pleasant xe2x80x9cfreshxe2x80x9d or xe2x80x9ccleanxe2x80x9d scent. In addition, as described herein above, the formulator may modify the pyranyl or furanyl portion of the pro-fragrance materials in order to provide increased fabric substantivity or laundry liquor solubility to the compounds which comprise the fragrance delivery system.
In general, the laundry detergent compositions of the present invention which have increased fragrance retention and fragrance longevity, comprise:
A) at least about 0.01%, preferably from about 0.01% to about 10%, more preferably from about 0.1% to about 1% by weight, of a fragrance delivery system comprising:
ii) one or more pro-fragrance compounds of the present invention;
iii) optionally fragrance carriers and other fragrance delivery adjuncts;
iv) optionally one or more releasable pro-fragrance materials;
B) at least about 0.01% by weight, preferably from about 0.1% to about 60%, more preferably from about 0.1% to about 30% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures thereof, preferably said surfactant is an anionic surfactant; and
C) the balance carriers and adjunct ingredients said adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach catalysts, bleach activators, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, enzymes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
For the purposes of the present invention the term xe2x80x9cone or more releasable pro-fragrance materialsxe2x80x9d described in section A (iv) above, is defined as other compounds which can suitably release a fragrance raw material, for example, as disclosed in U.S. Pat. No. 5,378,468 Suffis et al., issued Jan. 3, 1995, incorporated herein by reference.
In general, the rinse added fabric softening compositions of the present invention which have increased fragrance retention and fragrance longevity, comprise:
A) at least about 0.01%, preferably from about 0.01% to about 10%, more preferably from about 0.1% to about 1% by weight, of a fragrance delivery system comprising:
i) one or more pro-fragrance compounds according to the present invention;
ii) optionally one or more fragrance raw materials;
iii) optionally fragrance carriers and other fragrance delivery adjuncts;
B) from about 0.01%, preferably from about 85% to about 99.9% by weight of the composition, of ingredients useful for formulating fabric softening compositions, said ingredients selected from the group consisting of cationic fabric softening agents; nonionic fabric softening agents; liquid carrier; concentration aid; soil release agent; perfume; and preservatives/stabilizers, and mixtures thereof;
C) at least about 50% of a liquid carrier; and
D) optionally from about 0.01% to about 15% by weight, of concentration aids;
wherein further said compositions have a pH of less than about 6 at 20xc2x0 C.
In general, the dryer-added added fabric softening and fabric appearance benefit compositions are delivered by a article of manufacture such as a substrate, preferably a flexible substrate which is added to the dryer, said articles of manufacture comprise:
A) at least about 0.01%, preferably from about 0.01% to about 10%, more preferably from about 0.1% to about 1% by weight, of a fragrance delivery system comprising:
i) one or more pro-fragrance compounds according to the present invention;
ii) optionally one or more fragrance raw materials;
iii) optionally fragrance carriers and other fragrance delivery adjuncts;
B) a fabric treatment component comprising:
a) from about 1% to about 60% by weight, of a polyamine having the formula;
i) a polyamine having a backbone of the formula: 
wherein R is C2-C8 alkylene, C3-C8 alkyl substituted alkylene, and mixtures thereof, preferably ethylene, 1,2-propylene, 1,3-propylene, more preferably ethylene;
ii) a polyamine having a backbone of the formula: 
wherein y is from 5 to about 10,000; and
iii) optionally from 0% to 100% of the polyamine backbone NH units are substituted by one or more units having the formula:
xe2x80x94(R1O)XR2 
wherein R1 is C2-C6 alkylene, C3-C6 alkyl substituted alkylene, and mixtures thereof; R2 is hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen and methyl; wherein m is from 2 to about 700; n is from 0 to about 350; x is from 1 to 12, preferably from 1 to about 4; y is from 5 to 5000.
b) from about 40% to about 99% by weight, of a carboxylic acid carrier;
wherein the fabric treatment composition has a viscosity of less than about 2000 centipoise at 100xc2x0 C. and a melting point from about 25xc2x0 C. to about 95xc2x0 C.; and
C) dispensing means which provides for release of an effective amount of said polyamine (i) and carboxylic acid carrier (ii) to fabrics in an automatic laundry dryer at operating temperatures.
Surfactant Systems
The instant cleaning compositions may contain at least about 0.01% by weight of a surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic and zwitterionic surface active agents. Preferably the solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present invention, surfactant is preferably present to the extent of from about 0.1% to 60%, more preferably 0.1% to about 30% by weight of the composition.
Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight, include the conventional C11-C18 alkyl benzene sulfonates (xe2x80x9cLASxe2x80x9d) and primary, branched-chain and random C10-C20 alkyl sulfates (xe2x80x9cASxe2x80x9d), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3xe2x88x92M30)CH3 and CH3 (CH2)y(CHOSO3xe2x88x92M+) CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates (xe2x80x9cAExSxe2x80x9d; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates (xe2x80x9cAExe2x80x9d) including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines (xe2x80x9csultainesxe2x80x9d), C10-C18 amine oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides are highly preferred, especially the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are described further herein and are listed in standard texts.
Anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of fatty acids are derived from coconut oil sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
Additionally, secondary alkyl sulfates may be used by the formulator exclusively or in conjunction with other surfactant materials and the following identifies and illustrates the differences between sulfated surfactants and otherwise conventional alkyl sulfate surfactants. Non-limiting examples of such ingredients are as follows.
Conventional primary alkyl sulfates (AS), such as those illustrated above, have the general formula ROSO3xe2x88x92M+ wherein R is typically a linear C8-22 hydrocarbyl group and M is a water solublizing cation. Branched chain primary alkyl sulfate surfactants (i.e., branched-chain xe2x80x9cPASxe2x80x9d) having 8-20 carbon atoms are also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed Jan. 21, 1991.
Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl xe2x80x9cbackbonexe2x80x9d of the molecule. Such materials may be depicted by the structure
CH3(CH2)n(CHOSO3xe2x88x92M+)(CH2)mCH3 
wherein m and n are integers of 2 of greater and the sum of m+n is typically about 9 to 17, and M is a water-solublizing cation.
The aforementioned secondary alkyl sulfates are those prepared by the addition of H2SO4 to olefins. A typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued Feb. 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued Dec. 24,1991. See also U.S. Pat. No. 5,349,101, Lutz et al., issued Sep. 20, 1994; U.S. Pat. No. 5,389,277, Prieto, issued Feb. 14, 1995.
The preferred surfactants of the present invention are anionic surfactants, however, other surfactants useful herein are described below.
The compositions of the present invention can also comprise at least about 0.01%, preferably at least 0.1%, more preferably from about 1% to about 30%, of an nonionic detersive surfactant. Preferred nonionic surfactants such as C12-C18 alkyl ethoxylates (xe2x80x9cAExe2x80x9d) including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of C6 to C12 alkyl phenols, alkylene oxide condensates of C8-C22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic(trademark)-BASF Corp.), as well as semi polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions. An extensive disclosure of these types of surfactants is found in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, incorporated herein by reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. No. 4,565,647 Llenado (incorporated herein by reference) are also preferred nonionic surfactants in the compositions of the invention.
More preferred nonionic surfactants are the polyhydroxy fatty acid amides having the formula: 
wherein R7 is C5-C31 alkyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C15 alkyl or alkenyl, or mixtures thereof; R8 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof. Preferred Q is derived from a reducing sugar in a reductive amination reaction. More preferably Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Q. It should be understood that it is by no means intended to exclude other suitable raw materials. Q is more preferably selected from the group consisting of xe2x80x94CH2(CHOH)nCH2OH, xe2x80x94CH (CH2OH)(CHOH)n-1CH2OH, xe2x80x94CH2(CHOH)2-(CHORxe2x80x2)(CHOH)CH2OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and Rxe2x80x2 is hydrogen or a cyclic or aliphatic monosaccharide. Most preferred substituents for the Q moiety are glycityls wherein n is 4, particularly xe2x80x94CH2(CHOH)4CH2OH.
R7COxe2x80x94N less than  can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy ethyl, or 2-hydroxy propyl.
Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
A particularly desirable surfactant of this type for use in the compositions herein is alkyl-N-methyl glucomide, a compound of the above formula wherein R7 is alkyl (preferably C11-C17), R8, is methyl and Q is 1-deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used.
Buildersxe2x80x94Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called xe2x80x9cweakxe2x80x9d builders (as compared with phosphates) such as citrate, or in the so-called xe2x80x9cunderbuiltxe2x80x9d situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as xe2x80x9cSKS-6xe2x80x9d). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiO5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSixO2x+1xc2x7yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiO5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on Nov. 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
[Mz(zAlO2)y]xc2x7xH2O 
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, et al, issued Oct. 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na12[(AlO2)12(SiO2)12]xc2x7xH2O 
wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x=0-10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, xe2x80x9cpolycarboxylatexe2x80x9d refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, and Lamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also xe2x80x9cTMS/TDSxe2x80x9d builders of U.S. Pat. No. 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. No. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published Nov. 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No. 3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No. 3,723,322.
Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates (see, for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
Clay Soil Removal/Anti-Redeposition Agents
The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published Jun. 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published Jul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744, Connor, issued Oct. 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Other Ingredientsxe2x80x94A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar compositions, etc. Other optional ingredients include enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners, hydrolyzable surfactants, optical brighteners, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, soil release agents, germicides, fungicides, and anti corrosion agents. If high sudsing is desired, suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5xc3x97the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosity in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be xe2x80x9cprotectedxe2x80x9d for use in detergent compositions.
The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Granular Compositions
The pro-accords of the present invention can be used in both low density (below 550 grams/liter) and high density granular compositions in which the density of the granule is at least 550 grams/liter. Granular compositions are typically designed to provide an in the wash pH of from about 7.5 to about 11.5, more preferably from about 9.5 to about 10.5. Low density compositions can be prepared by standard spray-drying processes. Various means and equipment are available to prepare high density compositions. Current commercial practice in the field employs spray-drying towers to manufacture compositions which have a density less than about 500 g/l. Accordingly, if spray-drying is used as part of the overall process, the resulting spray-dried particles must be further densified using the means and equipment described hereinafter. In the alternative, the formulator can eliminate spray-drying by using mixing, densifying and granulating equipment that is commercially available. The following is a nonlimiting description of such equipment suitable for use herein.
Various means and equipment are available to prepare high density (i.e., greater than about 550, preferably greater than about 650, grams/liter or xe2x80x9cg/lxe2x80x9d), high solubility, free-flowing, granular detergent compositions according to the present invention. Current commercial practice in the field employs spray-drying towers to manufacture granular laundry detergents which often have a density less than about 500 g/l. In this procedure, an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175xc2x0 C. to about 225xc2x0 C. However, if spray drying is used as part of the overall process herein, additional process steps as described hereinafter must be used to obtain the level of density (i.e., greater than 650 g/l) required by modern compact, low dosage detergent products.
For example, spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers. A suitable high speed mixer/densifier for this process is a device marketed under the tradename xe2x80x9cLxc3x6dige CB 30xe2x80x9d or xe2x80x9cLxc3x6dige CB 30 Recyclerxe2x80x9d which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon. In use, the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See Jacobs et al, U.S. Pat. No. 5,149,455, issued Sep. 22, 1992. The preferred residence time in the high speed mixer/densifier is from about 1 to 60 seconds. Other such apparatus includes the devices marketed under the tradename xe2x80x9cShugi Granulatorxe2x80x9d and under the tradename xe2x80x9cDrais K-TTP 80).
Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower intraparticle porosity. Equipment such as that marketed under the tradename xe2x80x9cLxc3x6dige KMxe2x80x9d (Series 300 or 600) or xe2x80x9cLxc3x6dige Ploughsharexe2x80x9d mixer/densifiers are suitable for this process step. Such equipment is typically operated at 40-160 rpm. The residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes. Other useful equipment includes the device which is available under the tradename xe2x80x9cDrais K-T 160xe2x80x9d. This process step which employs a moderate speed mixer/densifier (e.g. Lxc3x6dige KM) can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e.g. Lxc3x6dige CB) to achieve the desired density. Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Pat. No. 2,306,898, to G. L. Heller, Dec. 29, 1942.
While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention. By way of example, see the processes in Appel et al, U.S. Pat. No. 5,133,924, issued Jul. 28, 1992 (granules are brought into a deformable state prior to densification); Delwel et al, U.S. Pat. No. 4,637,891, issued Jan. 20, 1987 (granulating spray-dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Pat. No. 4,726,908, issued Feb. 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Pat. No. 5,160,657, issued Nov. 3, 1992 (coating densified granules with a liquid binder and aluminosilicate).
In those situations in which particularly heat sensitive or highly volatile detergent ingredients or pro-accords are to be incorporated into the final detergent composition, processes which do not include spray drying towers are preferred. The formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing/densifying equipment that is commercially available. One particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material into a high speed mixer/densifier (e.g. Lxc3x6dige CB) followed by a moderate speed mixer/densifier (e.g. Lxc3x6dige KM) to form high density detergent agglomerates. See Capeci et al, U.S. Pat. No. 5,366,652, issued Nov. 22, 1994 and Capeci et al, U.S. Pat. No. 5,486,303, issued Jan. 23, 1996. Optionally, the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp.
Optionally, the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up. The oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment. These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density ( greater than 550 g/l). See Capeci et al, U.S. Pat. No. 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Pat. No. 5,489,392, issued Feb. 6, 1996. Other suitable processes which do not call for the use of spray-drying towers are described by Bollier et al, U.S. Pat. No. 4,828,721, issued May 9, 1989; Beerse et al, U.S. Pat. No. 5,108,646, issued Apr. 28, 1992; and, Jolicoeur, U.S. Pat. No. 5,178,798, issued Jan. 12, 1993.
In yet another embodiment, the high density detergent composition of the invention can be produced using a fluidized bed mixer. In this process, the various ingredients of the finished composition are combined in an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this process can optionally include the step of mixing the slurry using the aforementioned Lxc3x6dige CB mixer/densifier or a xe2x80x9cFlexomix 160xe2x80x9d mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename xe2x80x9cEscher Wyssxe2x80x9d can be used in such processes.
Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lxc3x6dige KM) for further agglomeration resulting in the finished high density detergent composition. See Appel et al, U.S. Pat. No. 5,164,108, issued Nov. 17, 1992.
Adjunct Cationic Conditioning Agents
Compositions of the present invention can contain from about 5% to about 95%, preferably from about 15% to about 90%, more preferably from about 25% to about 85%, and even more preferably from about 25% to about 55%, of biodegradable cationic softener, preferably an ester quaternary ammonium compound (EQA).
The optional fabric conditioning component is preferably a fabric softening compound which is an ester quaternary ammonium (EQA) compound or its precursor amine having the formula:
[(R1)4-pxe2x80x94N+xe2x80x94((CH2)vxe2x80x94Yxe2x80x94R2)p]Xxe2x88x92
wherein Y is a carboxy moiety having the formula 
the index p is from 1 to 3; the index v is from 1 to 4, and mixtures thereof; R1 is C1-C6 alkyl, C1-C4 hydroxy alkyl group, or benzyl, preferably C1-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; preferably one R1 moiety is a short chain alkyl group, preferably methyl; R2 is C8-C30 saturated alkyl or C8-C30 unsaturated alkyl, C8-C30 substituted alkyl or C8-C30 unsubstituted alkyl, preferably C14-C18 saturated alkyl or C14-C18 unsaturated alkyl, C14-C18 substituted alkyl or C14-C18 unsubstituted alkyl, more preferably linear C14-C18 saturated alkyl, wherein each R2 moiety suitable for use has an Iodine Value of from about 3 to about 60; the counter ion, Xxe2x88x92, can be any softener-compatible anion, preferably methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate, nitrate, benzoate, more preferably methylsulfate.
Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials.
It will be understood that substituents R1 and R2 of Formula I can optionally be substituted with various groups such as alkoxyl or hydroxyl groups. The preferred compounds can be considered to be diester (DEQA) variations of ditallow dimethyl ammonium methyl sulfate (DTDMAMS), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be EQA monoester (e.g., only one xe2x80x94Yxe2x80x94R2 group).
The following are non-limiting examples of EQA Formula I (wherein all long-chain alkyl substituents are straight-chain):
[C2H5]2+N[CH2CH2OC(O)C17H35]2 (CH3SO4)xe2x88x92
[CH3][C2H5]+N[CH2CH2OC(O)C13H27]2 [HC(O)O]xe2x88x92
[C3H7][C2H5 ]+N[CH2CH2OC(O)C11H23]2 (CH3 SO4)xe2x88x92[CH3]2+N-[CH2CH2OC(O)C17H35]CH2CH2OC(O)C15H31 (CH3SO4)xe2x88x92
[CH3]2+N[CH2CH2OC(O)R2]2 (CH3SO4)xe2x88x92
where xe2x80x94C(O)R2 is derived from saturated tallow.
[CH3]2+N[CH2CH2OC(O)C17H33]2 (CH3SO4)xe2x88x92
[C2H5]2+N[CH2CH2OC(O)C17H33]2 Clxe2x88x92
[CH3][C2H5]+N[CH2CH2OC(O)C13H25]2 [C6H5C(O)O]xe2x88x92
[CH3]2+N-[CH2CH2OC(O)C17H33]CH2CH2OC(O)C15H29 (CH3CH3CH2SO4)xe2x88x92
[CH3]2+N[CH2CH2OC(O)R2]2 (CH3SO4)xe2x88x92
where xe2x80x94C(O)R2 is derived from partially hydrogenated tallow or modified tallow having the characteristics set forth herein.
Other specific examples of biodegradable Formula I compounds suitable for use in the fabric softening compositions herein are:
N-methyl-N,N-di-(2-C14-C18-acyloxy ethyl);
N-2-hydroxyethyl ammonium methylsulfate;
[HOCH(CH3)CH2][CH3]+N[CH2CH2OC(O)C15H31]2 Brxe2x88x92;
[HOCH(CH3)CH2][CH3]+N[CH2CH2OC(O)C15H29]2 [HC(O)O]xe2x88x92; and
[CH2CH2OH][CH3]+N[CH2CH2OC(O)R2]2 (CH3SO4)xe2x88x92. A preferred compound is N-methyl, N,N-di-(2-oleyloxyethyl) N-2-hydroxyethyl ammonium methylsulfate.
Further suitable fabric softening compounds are quaternary ammonium compounds having the formula:
[(R14-pxe2x80x94N30 xe2x80x94((CH2)v-Yxe2x80x3xe2x80x94R2)p]Xxe2x88x92
wherein Yxe2x80x3 is a carboxy moiety having the formula 
and mixtures thereof, wherein at least one Yxe2x80x3 group is 
the index p is from 1 to 3; the index v is from 1 to 4, and mixtures thereof; R1 is C1-C6 alkyl or benzyl, preferably C1-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; preferably one R1 moiety is a short chain alkyl group, preferably methyl; R2 is C8-C30 saturated alkyl or C8-C30 unsaturated alkyl, C8-C30 substituted alkyl or C8-C30 unsubstituted alkyl, preferably C14-C18 saturated alkyl or C14-C18 unsaturated alkyl, C14-C18 substituted alkyl or C14-C18 unsubstituted alkyl, more preferably linear C14-C18 saturated alkyl, wherein each R2 moiety suitable for use has an Iodine Value of from about 3 to about 60; R3 is R or H; the counter ion, Xxe2x88x92, can be any softener-compatible anion, preferably methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate, nitrate, benzoate, more preferably methylsulfate.
It will be understood that substituents R and R2 of Formula II can optionally be substituted with various groups such as alkoxyl or hydroxyl groups.
The preferred ester linked compounds (DEQA) can be considered to be diester variations of ditallow dimethyl ammonium chloride (DTDMAC), which is a widely used fabric softener. Preferably, at least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be DEQA monoester (e.g., only one xe2x80x94Yxe2x80x94R2 group). For optimal antistatic benefit monoester should be low, preferably less than about 2.5%. The level of monoester can be controlled in the manufacturing of the DEQA.
The quaternary softening compounds with at least partially unsaturated alkyl or acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met. Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. Any reference to IV values hereinafter refers to IV of fatty alkyl or acyl groups and not to the resulting quaternary, e.g., DEQA compound. As the IV is raised, there is a potential for odor problems.
For unsaturated softener actives, the optimum storage temperature for stability and fluidity depends on the specific IV of, e.g., the fatty acid used to make DEQA and/or the level/type of solvent selected. Exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/handling of the material in manufacturing operations.
The following are non-limiting examples of DEQA Formula II (wherein all long-chain alkyl substituents are straight-chain):
[C2H5]2(+)N[CH2CH2OC(O)C17H35]2 SO4CH3(xe2x88x92)
[C3H7][C2H5](+)N[CH2CH2OC(O)C11H23]2 SO4(xe2x88x92)CH3 
[CH3]2(+)N[CH2CH2OC(O)R2]2 SO4CH3(xe2x88x92)
where xe2x80x94C(O)R2 is derived from saturated tallow.
[CH3]2(+)N[CH2CH2OC(O)C17H33]2 SO4(xe2x88x92)CH3 
[C2H5]2(+)N[CH2CH2OC(O)C17H33]2 Cl(xe2x88x92)
[CH2CH2OH][CH3](+)N[CH2CH2OC(O)R2]2 CH3SO4(xe2x88x92)
[CH3]2(+)N[CH2CH2OC(O)R2]2 CH3SO4(xe2x88x92)
where xe2x80x94C(O)R2 is derived from partially hydrogenated tallow or modified tallow having the characteristics set forth herein.
Further suitable fabric softening compounds according to the present invention are ester quaternary ammonium compounds having the formula: 
wherein Q is a carboxy moiety having the formula 
the index v is from 1 to 4, and mixtures thereof; R1 is C1-C4 alkyl, C1-C4 hydroxy alkyl group, preferably methyl; preferably one R1 moiety is a short chain alkyl group, preferably methyl; R2 is C8-C30 saturated alkyl or C8-C30 unsaturated alkyl, C8-C30 substituted alkyl or C8-C30 unsubstituted alkyl, preferably C14-C18 saturated alkyl or C14-C18 unsaturated alkyl, C14-C18 substituted alkyl or C14-C18 unsubstituted alkyl, more preferably linear C14-C18 saturated alkyl, wherein each R2 moiety suitable for use has an Iodine Value of from about 3 to about 60; the counter ion Xxe2x88x92is methylsulfate.
An example of the above described ester quaternary ammonium compound which is suitable for use as a fabric softening compound in the present invention is 1,2-bis(tallowyloxy)-3-trimethyl ammoniopropane methylsulfate (DTTMAPMS). Other suitable examples are 1,2-bis(cocoyloxy)-3-trimethyl ammoniopropane methylsulfate, 1,2-bis(lauryloxy)-3-trimethyl ammoniopropane methylsulfate, 1,2-bis(oleyloxy)-3-trimethyl ammoniopropane methylsulfate and 1,2-bis(stearyloxy)-3-trimethyl ammoniopropane methylsulfate. Replacing one or more or the methyl moieties in the above examples with ethyl, propyl, isopropyl, butyl, isobutyl, or mixtures thereof, result in suitable fabric softening compounds according to the present invention. In addition, other anions other than methylsulfate may be used.
Other examples of suitable Formula III EQA compounds of this invention are obtained by, e.g., replacing xe2x80x9ctallowylxe2x80x9d in the above compounds with, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing xe2x80x9cmethylxe2x80x9d in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals; replacing xe2x80x9cmethylsulfatexe2x80x9d in the above compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred.
Yet still further suitable fabric softening compounds according to the present invention are ester quaternary ammonium compounds having the formula: 
wherein Y is a carboxy moiety having the formula 
the index p is 2; the index v is from 1 to 4, and mixtures thereof; R1 is C1-C4 alkyl or hydroxy alkyl, preferably C1-C3 alkyl, for example, methyl, ethyl, propyl, most preferred is methyl; R2 is C8-C30 saturated or unsaturated, substituted or unsubstituted alkyl having an Iodine Value of from about 3 to about 60, preferred R2 is C8-C14 linear or branched alkyl, more preferred C8-C14 linear alkyl; R4 is a C1-C4 alcohol; the counter ion, Xxe2x88x92, can be any softener-compatible anion, preferably methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate, nitrate, benzoate, more preferably methylsulfate.
Most preferably, the quaternary ammonium compound is a fully saturated compound, such as dimethyl bis(tallowyloxyethyl) ammonium methylsulfate, derived from hardened tallow. Also suitable are dimethyl bis(acyloxyethyl) ammonium methylsulfate derivatives of C8-C30 fatty acids, such as dimethyl bis(tallowyloxyethyl) ammonium methylsulfate; dimethyl bis(oleyloxyethyl) ammonium methylsulfate or dimethyl bis(cocoyloxyethyl) ammonium methylsulfate. The composition of the present invention may comprise from about 15% to about 90% of these quaternary ammonium compounds.
An example of the above described ester quaternary ammonium compounds suitable for use as a fabric softening compound according to the present invention is N-methyl-N, N-bis-(2-C14-C18-acyloxy)ethyl-N-2-hydroxyethyl ammonium methylsulfate. A preferred example is N-methyl-N,N-bis(2-oleyloxyethyl)-N-(2-hydroxyethyl) ammonium methylsulfate.
The fabric conditioning composition can be any of those known in the art and/or previously disclosed by others in patent applications. Compositions that are suitable are disclosed in U.S. Pat. No. 3,944,694, McQueary; U.S. Pat. No. 4,073,996, Bedenk et al.; U.S. Pat. No. 4,237,155, Kardouche; U.S. Pat. No. 4,711,730, Gosselink et al.; 4,749,596, Evans et al.; 4,808,086, Evans et al.; 4,818,569, Trinh et al.; 4,877,896, Maldonado et al.; 4,976,879, Maldonado et al.; 5,041,230, Borcher, Sr. et al.; 5,094,761, Trinh et al.; 5,102,564, Gardlik et al.; and 5,234,610, Gardlik et al., all of said patents being incorporated herein by reference.
The compounds herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, incorporated herein by reference.
As used herein, when the diester quat is specified, it will include the monoester quat that is normally present. For the optimal antistatic benefit the percentage of monoester quat should be as low as possible, preferably less than about 20%. The level of monoester quat present can be controlled in the manufacturing of the EQA.
EQA compounds prepared with fully saturated acyl groups are rapidly biodegradable and excellent softeners. However, it has been discovered that compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met.
Variables that must be adjusted to obtain the benefits of using unsaturated acyl groups include the Iodine Value (IV) of the fatty acids, the odor of fatty acid starting material, and/or the EQA. Any reference to IV values herein refers to IV of fatty acyl groups and not to the resulting EQA compound.
Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. As the IV is raised, there is a potential for odor problems.
Some highly desirable, readily available sources of fatty acids such as tallow, possess odors that remain with the compound EQA despite the chemical and mechanical processing steps which convert the raw tallow to finished EQA. Such sources must be deodorized, e.g., by absorption, distillation (including stripping such as steam stripping), etc., as is well known in the art. In addition, care should be taken to minimize the adverse results of contact of the resulting fatty acyl groups with oxygen and/or bacteria by adding antioxidants, antibacterial agents, etc. The additional expense and effort associated with the unsaturated fatty acyl groups is justified by the superior performance.
Generally, hydrogenation of fatty acids to reduce polyunsaturation and to lower IV to insure good color and odor stability leads to a high degree of trans configuration in the molecule. Therefore, diester compounds derived from fatty acyl groups having low IV values can be made by mixing fully hydrogenated fatty acid with touch hydrogenated fatty acid at a ratio which provides an IV of from about 3 to about 60. The polyunsaturation content of the touch hardened fatty acid should be less than about 5%, preferably less than about 1%. During touch hardening the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high H2 availability, etc.
It has also been found that for good chemical stability of the diester quaternary compound in molten storage, water levels in the raw material must be minimized to preferably less than about 1% and more preferably less than about 0.5%. Storage temperatures should be kept as low as possible and still maintain a fluid material, ideally in the range of from about 49xc2x0 C. to about 75xc2x0 C. The optimum storage temperature for stability and fluidity depends on the specific IV of the fatty acid used to make the diester quaternary and the level/type of solvent selected. Also, exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/handling of the material in manufacturing operations.
Adjunct fabric softening compositions employed herein contain as an optional component, at a level of from about 0% to about 95%, preferably from about 20% to about 75%, more preferably from about 20% to about 60%, a carboxylic acid salt of a tertiary amine and/or ester amine which has the formula: 
wherein R5 is a long chain aliphatic group containing from about 8 to about 30 carbon atoms; R4 and R6 are the same or different and are independently selected from the group consisting of aliphatic groups containing from about 1 to about 30 carbon atoms, hydroxyalkyl groups of the formula R8OH wherein R8 is an alkylene group of from about 2 to about 30 carbon atoms, and polyalkyleneoxy moieties of the formula R9O(R10O)mxe2x88x92 wherein R9 is hydrogen, C1-C30 alkyl, C1-C30 alkenyl, and mixtures thereof; R10 is ethylene, 1,2 propylene, 1,3-propylene, and mixtures thereof; m is from about 2 to about 10; wherein further the R4, R5, R6, R8, and R9 chains can be ester interrupted groups; and wherein R7 is selected from the group consisting of C2-C30 linear alkyl, C2-C30 linear alkenyl, C8-C30 aryl, C8-C30 alkylaryl, and C8-C30 arylalkyl; substituted C1-C30 linear alkyl, C1-C30 linear alkenyl, C8-C30 aryl, C8-C30 alkylaryl, and C8-C30 arylalkyl wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl, said composition having a thermal softening point of from about 35xc2x0 C. to about 100xc2x0 C.
Preferably, R5 is an aliphatic chain containing from about C12-C30 linear alkyl, R6 is C12-C30 linear alkyl, and R4 is C1-C30 linear alkyl.
Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallow-dimethylamine, coconutdimethyl-amine, dilaurylmethylamine, distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethyl-methylamine, and 
Preferred fatty acids are those wherein R7 is C8-C30 linear alkyl, more preferably C11-C17 linear alkyl.
Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic acid, 3-chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl)benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4-hydroxyphenyl)acetic acid, and phthalic acid.
Preferred carboxylic acids are stearic, oleic, lauric, myristic, pahnitic, and mixtures thereof.
The amine salt can be formed by a simple addition reaction, well known in the art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980, which is incorporated herein by reference. Excessive levels of free amines may result in odor problems, and generally free amines provide poorer softening performance than the amine salts.
Preferred amine salts for use herein as optional ingredients are those wherein the amine moiety is a C8-C30 alkyl or alkenyl dimethyl amine or a di-C8-C30 alkyl or alkenyl methyl amine, and the acid moiety is a C8-C30 alkyl or alkenyl monocarboxylic acid. The amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, since these materials are normally derived from natural fats and oils, or synthetic processed which produce a mixture of chain lengths. Also, it is often desirable to utilize mixtures of different chain lengths in order to modify the physical or performance characteristics of the softening composition.
Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimethylamine stearate, stearyldimethylamine myristate, stearyldimethylamine oleate, stearyldimethylamine palmitate, distearyhnethylamine palmitate, distearylmethylamine laurate, and mixtures thereof. A particularly preferred mixture is oleyldimethylamine stearate and distearylmethylamine myristate, in a ratio of 1:10 to 10:1, preferably about 1:1.
Adjunct Nonionic Conditioning Agents
An optional softening agent of the present invention is a nonionic fabric softener material. Typically, such nonionic fabric softener materials have an HLB of from about 2 to about 9, more typically from about 3 to about 7. In general, the materials selected should be relatively crystalline, higher melting, (e.g.,  greater than 25xc2x0 C.).
The level of optional nonionic softener in the solid composition is typically from about 10% to about 50%, preferably from about 15% to about 40%.
Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety contains from about 8 to about 30, preferably from about 12 to about 20, carbon atoms. Typically, such softeners contain from about one to about 3, preferably about 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, penta-erythritol, sorbitol or sorbitan.
The fatty acid portion of the ester is normally derived from fatty acids having from about 8 to about 30, preferably from about 12 to about 22, carbon atoms. Typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid.
Highly preferred optional nonionic softening agents for use in the present invention are C10-C26 acyl sorbitan esters and polyglycerol monostearate. Sorbitan esters are esterified dehydration products of sorbitol. The preferred sorbitan ester comprises a member selected from the group consisting of C10-C26 acyl sorbitan monoesters and C10-C26 acyl sorbitan diesters and ethoxylates of said esters wherein one or more of the unesterified hydroxyl groups in said esters contain from 1 to about 6 oxyethylene units, and mixtures thereof. For the purpose of the present invention, sorbitan esters containing unsaturation (e.g., sorbitan monooleate) can be utilized.
Sorbitol, which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No. 2,322,821, Brown, issued Jun. 29, 1943, incorporated herein by reference.)
The foregoing types of complex mixtures of anhydrides of sorbitol are collectively referred to herein as xe2x80x9csorbitan.xe2x80x9d It will be recognized that this xe2x80x9csorbitanxe2x80x9d mixture will also contain some free, uncyclized sorbitol.
The preferred sorbitan softening agents of the type employed herein can be prepared by esterifying the xe2x80x9csorbitanxe2x80x9d mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or fatty acid. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from such reactions, and the stoichiometric ratios of the reactants can be simply adjusted to favor the desired reaction product.
For commercial production of the sorbitan ester materials, etherification and esterification are generally accomplished in the same processing step by reacting sorbitol directly with fatty acids. Such a method of sorbitan ester preparation is described more fully in MacDonald; xe2x80x9cEmulsifiers:xe2x80x9d Processing and Quality Control:, Journal of the American Oil Chemists""Society, Vol. 45, October 1968.
Details, including formula, of the preferred sorbitan esters can be found in U.S. Pat. No. 4,128,484, incorporated hereinbefore by reference.
Certain derivatives of the preferred sorbitan esters herein, especially the xe2x80x9clowerxe2x80x9d ethoxylates thereof (i.e., mono-, di-, and tri-esters wherein one or more of the unesterified xe2x80x94OH groups contain one to about twenty oxyethylene moieties (Tweens(copyright)) are also useful in the composition of the present invention. Therefore, for purposes of the present invention, the term xe2x80x9csorbitan esterxe2x80x9d includes such derivatives.
The material which is sold commercially as sorbitan mono-ester (e.g., monostearate) does in fact contain significant amounts of di- and tri-esters and a typical analysis of sorbitan monostearate indicates that it comprises about 27% mono-, 32% di-and 30% tri- and tetra-esters. Commercial sorbitan monostearate therefore is a preferred material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are useful. Both the 1,4- and 1,5-sorbitan esters are useful herein.
Other useful alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly the 1,4- and 1,5-sorbitans, with the corresponding acid, ester, or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials prepared in this manner will comprise mixtures usually containing minor proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and the like. In the present invention, it is preferred that such impurities are present at as low a level as possible.
The preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of the C20-C26, and higher, fatty acids, as well as minor amounts of C8, and lower, fatty esters.
Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-, are also preferred herein (e.g., polyglycerol monostearate with a trade name of Radiasurf 7248). Glycerol esters can be prepared from naturally occurring triglycerides by normal extraction, purification and/or inter-esterification processes or by esterification processes of the type set forth hereinbefore for sorbitan esters. Partial esters of glycerin can also be ethoxylated to form usable derivatives that are included within the term xe2x80x9cglycerol esters.xe2x80x9d
Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.
The xe2x80x9cglycerol estersxe2x80x9d also include the polyglycerol, e.g., diglycerol through octaglycerol esters. The polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages. The mono-and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
The dryer activated fabric softening compositions of the present invention may further includes a co-softener. The co-softener may comprise a carboxylic acid salt of a tertiary amine, tertiary amine ester, or mixtures thereof. The carboxylic acid salt forming anion moiety of the co-softener may be selected from the group consisting of lauric, myristic, palmitic, stearic, oleic and mixtures thereof. The amine salt of the co-softener may be selected from the group consisting of oleyldimethylamine stearate, dioleyl-methylamine stearate, linoleyldimethylamine stearate, dilinoleylmethylamine stearate, stearyldimethylamine stearate, distearylmethylamine myristate, stearyldimethylamine palmitate, distearyhnethylamine palmitate, distearylmethylamine myristate, distearyl-methylamine palmitate, distearylmethylamine laurate, dioleyldistearylmethylamine oleate, distearylmethyl-amine oleate, and mixtures thereof.
Optional Cyclodextrin/Perfume Complexes and Free Perfume
The products herein can also contain from about 0.5% to about 60%, preferably from about 1% to about 50%, cyclodextrin/perfume inclusion complexes and/or free perfume, as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al., issued Aug. 18, 1992; and 5,234,610, Gardlik et al., to issue Aug. 10, 1993, which are incorporated herein by reference. Perfumes are highly desirable, can usually benefit from protection, and can be complexed with cyclodextrin. Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective.
The optional perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. No. 4,145,184, Brain and Cummins, issued Mar. 20, 1979; U.S. Pat. No. 4,209,417, Whyte, issued Jun. 24, 1980; U.S. Pat. No. 4,515,705, Moeddel, issued May 7, 1985; and U.S. Pat. No. 4,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference. Many of the art recognized perfume compositions are relatively substantive to maximize their odor effect on substrates. However, it is a special advantage of perfume delivery via the perfume/cyclodextrin complexes that nonsubstantive perfumes are also effective.
If a product contains both free and complexed perfume, the escaped perfume from the complex contributes to the overall perfume odor intensity, giving rise to a longer lasting perfume odor impression.
As disclosed in U.S. Pat. No. 5,234,610, Gardlik/Trinh/Banks/Benvegnu, issued Aug. 3, 1993, said patent being incorporated herein by reference, by adjusting the levels of free perfume and perfume/CD complex it is possible to provide a wide range of unique perfume profiles in terms of timing (release) and/or perfume identity (character). Solid, dryer-activated fabric conditioning compositions are a uniquely desirable way to apply the cyclodextrins, since they are applied at the very end of a fabric treatment regimen when the fabric is clean and when there are almost no additional treatments that can remove the cyclodextrin.
Stabilizers
Stabilizers can be present in the compositions of the present invention. The term xe2x80x9cstabilizer,xe2x80x9d as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.05% to about 0.1% for antioxidants and more preferably from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions for the compositions. Use of antioxidants and reductive agent stabilizers is especially advantageous for low scent products (low perfume).
Examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox(copyright) PG and Tenox S-1; a mixture of BHT, BHA, propyl gallate, and citric acid available from Eastman Chemicals Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane(copyright) BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA.
Examples of reductive agents include sodium borohydride, hypophosphorous acid, and mixtures thereof.
Other Adjunct Ingredients
The present invention can include other adjunct components (minor components) conventionally used in textile treatment compositions, for example, colorants, perfumes, perfume systems, preservatives, optical brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and the like.
In preferred embodiments, the present invention encompasses articles of manufacture. Representative articles are those that are adapted to soften fabrics in an automatic laundry dryer, of the types disclosed in U.S. Pat. No. 3,989,631, Marsan, issued Nov. 2, 1976; U.S. Pat. No. 4,055,248, Marsan, issued Oct. 25, 1977; U.S. Pat. No. 4,073,996, Bedenk et al., issued Feb. 14, 1978; U.S. Pat. No. 4,022,938, Zaki et al., issued May 10, 1977; U.S. Pat. No. 4,764,289, Trinh, issued Aug. 16, 1988; U.S. Pat. No. 4,808,086, Evans et al., issued Feb. 28,1989; U.S. Pat. No. 4,000,340, Murphy et al., issued Dec. 28, 1976; U.S. Pat. No. 4,103,047, Zaki et al., issued Jul. 25, 1978; U.S. Pat. No. 3,736,668, Dillarstone, issued Jun. 5, 1973; U.S. Pat. No. 3,701,202, Compa et al., issued Oct. 31, 1972; U.S. Pat. No. 3,634,947, Furgal, issued Jan. 18, 1972; U.S. Pat. No. 3,633,538, Hoeflin, issued Jan. 11, 1972; U.S. Pat. No. 3,435,537, Rumsey, issued Apr. 1, 1969; all of which are incorporated herein by reference.